CN112996773B - 一种含硫联苯类化合物的制备方法 - Google Patents
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- CN112996773B CN112996773B CN201980062129.6A CN201980062129A CN112996773B CN 112996773 B CN112996773 B CN 112996773B CN 201980062129 A CN201980062129 A CN 201980062129A CN 112996773 B CN112996773 B CN 112996773B
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 16
- 239000011593 sulfur Substances 0.000 title claims abstract description 16
- -1 biphenyl compound Chemical class 0.000 title claims abstract description 15
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 12
- 239000004305 biphenyl Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 31
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 26
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical group [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Chemical group 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 150000001555 benzenes Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 8
- 239000005457 ice water Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 3
- 230000000895 acaricidal effect Effects 0.000 description 3
- 239000000642 acaricide Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 3
- BJXYOCZUBZGOIZ-UHFFFAOYSA-N 1-bromo-2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)benzene Chemical compound CC1=CC(F)=C(Br)C=C1SCC(F)(F)F BJXYOCZUBZGOIZ-UHFFFAOYSA-N 0.000 description 2
- GDGFKAGHOJMLIX-UHFFFAOYSA-N 1-chloro-2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)benzene Chemical compound CC1=CC(=C(C=C1SCC(F)(F)F)Cl)F GDGFKAGHOJMLIX-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 125000004649 C2-C8 alkynyl group Chemical group 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000006450 cyclopropyl cyclopropyl group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QEKXARSPUFVXIX-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dibromide Chemical compound [Ni+2].[Br-].[Br-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QEKXARSPUFVXIX-UHFFFAOYSA-L 0.000 description 1
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/10—Sulfones; Sulfoxides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/02—Acaricides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- General Health & Medical Sciences (AREA)
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- Insects & Arthropods (AREA)
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Abstract
一种制备如通式(I)所示的一种含硫联苯类化合物的方法,反应式如式aa,
Description
技术领域
本发明属于有机合成领域,具体地涉及一种含硫联苯类化合物的制备方法。
背景技术
含硫联苯类化合物是一类高效的新型杀螨剂。CN105541682A中公开了如其通式I所示的含硫联苯类化合物,该类化合物对朱砂叶螨表现了优异的杀螨活性。CN105541682A报道了该类化合的合成方法,芳基碘苯与联硼酸频哪醇酯在适宜的有机溶剂中、适宜的碱作用下,采用钯催化剂偶联制得目标物。具体反应式如下:
一直以来,技术人员致力于不断研究开发新的、更为先进合理、更加环保的制备方法,以便以更优的质量、更低的价格获得高效、安全的含硫联苯类杀螨剂。
发明内容
本发明的目的在于提供一种适合大规模工业化生产的含硫联苯类化合物的制备方法。
为实现上述目的,本发明采用技术方案为:
一种含硫联苯类化合物的制备方法,通式(I)所示的含硫联苯类化合物的方法,反应式如下:
式中:R选自C1-C8烷基、卤代C1-C8烷基、C2-C8烯基、卤代C2-C8烯基、C2-C8炔基、卤代C2-C8炔基;X选自氯、溴;m选自0、1、2。
所述通式(II)所示的化合物,在由镍化合物、至少一种配体组成的催化体系,与金属锌共同作用下发生偶联反应,制得通式(I)所示化合物。
所述反应条件为所述通式(II)所示的化合物与镍化合物、配体、金属锌于适宜的溶剂中、温度为20℃至所选溶剂沸点范围内,进行偶联反应1-24小时,制得通式(I)所示化合物。
所述的溶剂选自甲苯、乙酸乙酯、乙腈、四氢呋喃、二氧六环、丙酮、丁酮、二甲基甲酰胺或二甲基亚砜。
上述偶联反应中还可加入活化添加剂,活性添加剂的添加量为所述通式(II)所示化合物摩尔量的1%-15%;其中,活性添加剂为金属的卤代物、金属的硫酸盐或金属的磷酸盐,上述活性添加剂中所提及的金属均为碱金属、碱土金属、锰或铝。
所述镍化合物选自氯化镍、溴化镍、双(三苯基膦)氯化镍或双(三苯基膦)溴化镍,添加量为所述通式(II)所示化合物摩尔量的1%-10%;配体选自三芳基膦,其中芳基选自C6-C34芳基,添加量为所述通式(II)所示化合物摩尔量的20%-100%;金属锌的量为所述通式(II)所示化合物摩尔量的50%-200%。
所述镍化合物选自氯化镍,添加量为所述通式(II)所示化合物摩尔量的2%-5%;配体选自三苯基膦,添加量为通式(II)所示化合物摩尔量的40%-60%;活化添加剂选自碱金属的卤代物,添加量为所述通式(II)所示化合物摩尔量的5%-10%;金属锌的量为所述通式(II)所示化合物摩尔量的100%-150%。
所述活化添加剂选自溴化钠、溴化钾、碘化钠或碘化钾。
进一步的说上述制备方法反应式中,R选自甲基、乙基、环丙基、三氟甲基、CH2CF3、CH2CHF2、CH2CH2F、CH2CH=CF2或者CH2CN;X选自氯、溴;m选自0、1时,镍化合物选自氯化镍或溴化镍;活化添加剂选自碱金属的卤代物;配体选自三苯基膦。
再进一步的说上述制备方法反应式中,R选自CH2CF3;X选自氯;m独立选自0时,镍化合物选自氯化镍;活化添加剂选自溴化钠、溴化钾、碘化钠、碘化钾;配体选自三苯基膦。
并且通式(II)所示化合物中氯代或溴代芳基苯类的制备参见WO2014202505A1中描述的方法。
同时,上述制备过程中反应式中当m=1或2时,通式(I)所示化合物即为亚砜或砜类化合物,其还可通过按上述方法制备获得m=0的联苯硫醚化合物与合适的氧化剂反应制得;其中,合适的氧化剂选自过氧化苯甲酸、双氧水或(偏)高碘酸钠。
上面给出的合成方法及各通式化合物中基团的定义中,汇集所用术语一般定义如下:
烷基是指直链或支链形式,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、特丁基、正戊基、异戊基等基团。环烷基是指包括环状链形式,例如环丙基、环丁基、环戊基、环己基、甲基环丙基、环丙基环丙基等基团。烯基是指直链或支链烯基,如1-丙烯基、2-丙烯基和不同的丁烯基和戊烯基基异构体。卤素是指氟、氯、溴、碘。
同现有技术相比,本发明所具有的优点:
本发明式(I)所示的含硫联苯类化合物是一类高效、安全的新型杀螨剂,为了寻找适合含硫联苯类化合物大规模工业化生产的方法,本发明采用更加廉价易得的氯代或溴代苯作为原料,代替了原来的碘代苯。采用价格低廉的镍化合物作为催化剂,代替了价格昂贵的钯催化剂;因此本发明的新方法更适合大规模的工业化生产。
具体实施方式
下列实施例用于详细说明本发明所示的通式(I)的制备方法,但不意味着限制本发明。在本发明的权利要求所限定的范围内,可进行各种变换和改动。
本发明制备过程中用取代氯苯或溴苯在廉价的镍化合物和有机膦配体组成的催化体系,与廉价的金属锌共同作用下发生偶联反应,制得通式I所示的含硫联苯类化合物。
实施例1
2,2′-二氟-4,4′-二甲基-5,5′-二(2,2,2-三氟乙硫基)-1,1′-联苯的合成
向反应瓶中加入三苯基磷(13.23g,0.05moL)、溴化钠(1.55g,0.015moL)、锌粉(6.56g,0.1moL)、氯化镍(0.65g,0.005moL)。通入氮气置换空气,在室温、氮气保护条件下,不开启搅拌,向反应瓶滴入12.5mL DMF,滴加时间5min,物料局部变红色,再加入50mL DMF,温度升至60℃继续搅拌1h。滴加2-氟-4-甲基-5-三氟乙硫基溴苯(30.9g,0.1moL)与DMF的混合物(30.9g溶于15mL DMF中),滴加时间约2h。滴完后保温40~45℃至反应完毕。反应结束后,降温,过滤(硅藻土助滤),滤液减压浓缩后加入50mL甲苯、50mL水,静置,分层。有机层移入反应瓶中,冰水浴冷却,向有机层滴加双氧水(5.7g,0.05moL),滴加时间约0.5h,滴加完毕后于40℃保温1h,取样分析三苯基膦完全转化为三苯基氧膦,降至室温,过滤除去三苯基氧膦,滤饼用甲苯(15mL)洗涤,滤液分层,减压下蒸出甲苯,加入15g乙醇,升温至固体全部溶解,冰水降温至10℃以下,不断有固体洗出,过滤,烘干后得到目标化合物白色固体19.15g,熔点:64.2-65.1℃。HPLC定量含量99%,收率为85%。1H NMR(300MHz,CDCl3):7.55(t,2H),7.06(t,2H),3.33(q,4H),2.52(s,6H).[M]=446.6(GC-MS)。
实施例2
2,2′-二氟-4,4′-二甲基-5,5′-二(2,2,2-三氟乙硫基)-1,1′-联苯的合成
向反应瓶中加入三苯基磷(13.23g,0.05moL)、碘化钾(1.64g,0.01moL)、锌粉(6.56g,0.1moL)、氯化镍(0.65g,0.005moL)。通入氮气置换空气,在室温、氮气保护条件下,不开启搅拌,向反应瓶滴入12.5mL DMF,滴加时间5min,物料局部变红色,再加入50mL DMF,温度升至40℃继续搅拌1h。滴加2-氟-4-甲基-5-三氟乙硫基氯苯(26.1g,0.1moL)与DMF的混合物(26.1g溶于15mL DMF中),滴加时间约2h。滴完后保温55~60℃至反应完毕。反应结束后,降温,过滤(硅藻土助滤),滤液减压浓缩后加入50mL甲苯、50mL水,静置,分层。有机层移入反应瓶中,冰水浴冷却,向有机层滴加双氧水(5.7g,0.05moL),滴加时间约0.5h,滴加完毕后于40℃保温1h,取样分析三苯基膦完全转化为三苯基氧膦,降至室温,过滤除去三苯基氧膦,滤饼用甲苯(15mL)洗涤,滤液分层,减压下蒸出甲苯,加入14g乙醇,升温至固体全部溶解,冰水降温至10℃以下,不断有固体洗出,过滤,烘干后得到目标化合物白色固体18.66g,熔点:64.2-65.1℃。HPLC定量含量98%,收率为82%。1H NMR(300MHz,CDCl3):7.55(t,2H),7.06(t,2H),3.33(q,4H),2.52(s,6H).[M]=446.6(GC-MS)。
实施例3
2,2′-二氟-4,4′-二甲基-5,5′-二(2,2,2-三氟乙硫基)-1,1′-联苯的合成
向反应瓶中加入三苯基磷(13.23g,0.05moL)、碘化钠(0.75g,0.005moL)、锌粉(6.56g,0.1moL)、溴化镍(1.09g,0.005moL)。通入氮气置换空气,在室温、氮气保护条件下,不开启搅拌,向反应瓶滴入12.5mL DMF,滴加时间5min,物料局部变红色,再加入50mL DMF,温度升至40℃继续搅拌1h。滴加2-氟-4-甲基-5-三氟乙硫基氯苯(26.1g,0.1moL)与DMF的混合物(26.1g溶于15mL DMF中),滴加时间约2h。滴完后保温50~55℃至反应完毕。反应结束后,降温,过滤(硅藻土助滤),滤液减压浓缩后加入50mL甲苯、50mL水,静置,分层。有机层移入反应瓶中,冰水浴冷却,向有机层滴加双氧水(5.7g,0.05moL),滴加时间约0.5h,滴加完毕后于40℃保温1h,取样分析三苯基膦完全转化为三苯基氧膦,降至室温,过滤除去三苯基氧膦,滤饼用甲苯(15mL)洗涤,滤液分层,减压下蒸出甲苯,加入15g乙醇,升温至固体全部溶解,冰水降温至10℃以下,不断有固体洗出,过滤,,烘干后得到目标化合物,白色固体18.90g,熔点:64.2-65.1℃。HPLC定量含量98%,收率约83%。1H NMR(300MHz,CDCl3):7.55(t,2H),7.06(t,2H),3.33(q,4H),2.52(s,6H).[M]=446.6(GC-MS)。
实施例4
2,2′-二氟-4,4′-二甲基-5,5′-二(2,2,2-三氟乙硫基)-1,1′-联苯的合成
向反应瓶中加入三苯基磷(534.7g,2moL)、溴化钠(42.04g,0.4moL)、锌粉(265.3g,4moL)、氯化镍(18.13g,0.14moL)。通入氮气置换空气,在室温、氮气保护条件下,不开启搅拌,向反应瓶滴入1200mL DMF,滴加时间30min,物料局部变红色,再加入1200mLDMF,温度升至60℃继续搅拌1h。滴加2-氟-4-甲基-5-三氟乙硫基溴苯(1236g,4moL)与DMF的混合物(1236g溶于600mL DMF中),滴加时间约2h。滴完后保温40~45℃至反应完毕。反应结束后,降温,过滤(硅藻土助滤),滤液减压浓缩后加入3000mL甲苯、2500mL水,静置,分层。有机层移入反应瓶中,冰水浴冷却,向有机层滴加双氧水(226.7g,2moL),滴加时间约2h,滴加完毕后于40℃保温1h,取样分析三苯基膦完全转化为三苯基氧膦,降至室温,过滤除去三苯基氧膦,滤饼用甲苯(500mL)洗涤,滤液分层,减压下蒸出甲苯,加入700g乙醇,升温至固体全部溶解,冰水降温至10℃以下,不断有固体洗出,过滤,烘干后得到目标化合物白色固体787.1g,熔点:64.2-65.1℃。HPLC定量含量98.6%,收率为87%。1H NMR(300MHz,CDCl3):7.55(t,2H),7.06(t,2H),3.33(q,4H),2.52(s,6H).[M]=446.6(GC-MS)。
同时按照上述具体的制备方法,仅是是对一些条件进行替换还可制备下述表1所述的其它化合物,具体为镍化合物选自氯化镍或溴化镍;活化添加剂选自碱金属的卤代物;配体选自三苯基膦。
表1.部分通式(I)化合物的结构
Claims (2)
1.一种含硫联苯类化合物的制备方法,其特征在于:通式(I)所示的含硫联苯类化合物的方法,反应式如下:
式中:R选自CH2CF3;X选自氯、溴;m选自0;
所述反应条件为所述通式(II)所示的化合物与镍化合物、配体、金属锌于适宜的溶剂中、温度为40℃至60℃范围内,进行偶联反应1-24小时,制得通式(I)所示化合物;
所述镍化合物选自氯化镍、溴化镍,添加量为所述通式(II)所示化合物摩尔量的2%-5%;配体选自三苯基膦,添加量为所述通式(II)所示化合物摩尔量的40%-60%;金属锌的量为所述通式(II)所示化合物摩尔量的100%-150%;
所述偶联反应中加入活化添加剂,所述活化添加剂选自溴化钠、溴化钾、碘化钠或碘化钾,添加量为所述通式(II)所示化合物摩尔量的5%-10%;
所述通式(II)所示的化合物采用滴加方式。
2.按权利要求1所述的含硫联苯类化合物的制备方法,其特征在于:所述的溶剂选自二甲基甲酰胺或二甲基亚砜。
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